Cyclopropanecarboxylate pesticides

ABSTRACT

Compounds of the formula   &lt;IMAGE&gt;   wherein R1 is a hydrocarbyl group, W is a chlorine or bromine atom or -OR in which R is H, a salt-forming cation, an alkyl group or the residue of a pyrethroid alcohol are new pesticides or intermediates therefore. The compounds are prepared using a multi-step synthesis starting from the natural terpene, 3-carene.

This is a division of application Ser. No. 50,735 filed in June 21,1979.

This case covers the following compounds:

    ______________________________________                                         ##STR2##                                                                                                        Embodi-                                    SD No. R.sup.1    R                ment                                       ______________________________________                                        57843  CH(CH.sub.3).sub.2                                                                       H                I                                          57972  CH(CH.sub.3).sub.2                                                                       α-cyano-3-phenoxybenzyl                                                                  II a                                       57973  CH(CH.sub.3).sub.2                                                                       α-cyano-3-phenoxybenzyl                                                                  II b                                       ______________________________________                                    

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention is directed to new cyclopropane compounds, theiruse in pest control and to pest control formulations containing the newcyclopropanecarboxylates.

2. Summary of the Invention

The present invention relates to new cyclopropane compounds of theformula ##STR3## wherein R¹ is an alkyl group containing from 1 to 10carbon atoms optionally substituted by one or more halogen atoms; a(cycloalkyl)alkyl group containing from 3 to 7 ring carbon atoms, atotal of from 4 to 9 carbon atoms and optionally ring-substituted by oneor more halogen atoms; a cycloalkyl group containing from 3 to 7 ringcarbon atoms; an alkenyl group containing from 2 to 4 carbon atomsoptionally substituted by one or more halogen atoms; an alkynyl groupcontaining from 2 to 4 carbon atoms or an aryl group containing from 6to 12 carbon atoms or an aralkyl group containing from 7 to 10 carbonatoms, each optionally ring-substituted by one or more halogen atoms; Wis a chlorine or bromine atom or --OR in which R is a hydrogen atom, asaltforming cation, an alkyl group containing from 1 to 20 carbon atomsor a group of the formula ##STR4## wherein Y represents hydrogen or analkyl, alkenyl or alkynyl group or an aryl or furyl group which isunsubstituted or substituted in the ring by one or more alkyl, alkenyl,alkoxy or halogeno groups, R⁷ and R⁸, which may be the same ordifferent, each represent hydrogen or an alkyl or alkenyl group, R⁹represents hydrogen or a methyl group, R¹⁰ and R¹¹ represent hydrogen oran alkyl group, R¹² represents an organic radical having carbon-carbonunsaturation in a position α to the CH₂ group to which R¹² is attached,A/S indicates an aromatic ring or a dihydro or tetrahydro analoguethereof, X¹, X², X³ and X⁴, which may be the same or different, eachrepresents hydrogen, halogen or a methyl group, D represents H, --CN,--C.tbd.CH or ##STR5## in which R¹³ and R¹⁴ may be the same ordifferent, each represent a hydrogen atom or an alkyl group containingfrom 1 to 10 carbon atoms, Z represents --CH₂ --, --O--, --CO-- or--S--, Z¹ and Z², which may be the same or different, each representhalogen or an alkyl group containing 1 to 4 carbon atoms and n is 0 , 1or 2, R³ and R⁴ each independently is a hydrogen atom, a halogen atomhaving an atomic number of from 9 to 35, inclusive, an alkyl groupcontaining from 1 to 4 carbon atoms or a nitro group, R⁵ is a hydrogenatom or a halogen atom, each R⁶ is a halogen atom having an atomicnumber of from 9 to 35, inclusive, each X⁵ is independently a halogenatom and m is an integer of from 1 to 5, with the proviso that when D is--CN, --C.tbd.CH or then the alcohol moiety is in the R,S-racemic or inthe S-optical configuration.

In the above formulas, suitable halogen atoms substituents are chlorine,fluorine or bromine.

The cyclopropane compounds exhibit geometrical and optical isomerism byvirture of the double bond and the two asymmetric centers in thecyclopropane ring. Consequently, the compounds can be prepared inoptically active forms, which can subsequently be mixed together, or asracemic mixtures, which can subsequently be prepared as optically activeforms. Because they usually provide the highest degree of pest control,the (1R,cis) esters are preferred although the (1R,trans) esters arealso active. In the esters of α-substituted alchols in which D informulas I, IV or VII is other than hydrogen, there is a furtherpossibility of optical isomerism, i.e., as R or as S opticalconfiguraton; the former are without practical pest control activity. Inaddition, optically active forms can be separated into the individualgeometrical isomers.

Examples of species within the scope of the present invention include:

α-cyano-3-phenoxybenzyl2,2-dimethyl-3--(2-(isobutoxyimino)propyl)cyclopropanecarboxylate,

5-benzyl-3-furylmethyl2,2-dimethyl-3-(2-(neopentoxyimino)propyl)cyclopropanecarboxylate,

α-ethynyl-3-phenoxybenzyl2,2-dimethyl-3-(2-(cyclopropylmethoxyimino)propyl)cyclopropanecarboxylate,

α-thiocarbamoyl-3-phenoxybenzyl2,2-dimethyl-3-(2-(propargyloxyimino)propyl)cyclopropanecarboxylate.

3-benzylbenzyl2,2-dimethyl-3-(2-(trichloroethoxyimino)propyl)cyclopropanecarboxylateand

3-phenylthiobenzyl2,2-dimethyl-3-(2-(p-chlorophenoxyimino)propyl)cyclopropanecarboxylates.

Matsui et al., Agr. Biol. Chem., 29, No. 8, p. 784--6, (1965) disclosesthe preparation of 2,2-dimethyl-3(2-oxopropyl)cyclopropanecarboxylicacid of formula X ##STR6## from Δ³ -carene.

Treatment of an aqueous, preferably buffered, solution of this acid withhydroxylamine or a hydrocarbyloxyamine of the formula R¹ NHOH or an acidaddition salt thereof yields the corresponding noveloxyimino-substituted acid of the invention wherein W is OH.

The alcohols of the groups of formulas I through IX, inclusive, areknown in the art, as for example in Elliott et al., U.S. Pat. No.3,567,740 and 3,922,269 or Belgian Pat. No. 839,360 and 862,109. Thepest control esters of the present invention can be prepared byesterification involving the reaction of an alcohol or derivativethereof of formula RQ, e.g., of formula XI, and a cyclopropanecarboxylicacid or derivative of formula XII ##STR7## wherein Q and COP arefunctional groups or atoms which will react to form an ester linkage andR¹, D, Z, Z¹ and Z² are defined above.

It is usually convenient in practice either to treat the acid or acidhalide with the alcohol (COP═COOH or CO-halide and Q═OH) or to treat ahalogeno compound (Q=halogen) with a salt of the carboxylic acid(COP--COO--M) where M is, for example, a silver or ammonium cation.

Suitable routes to the esters in which D is ##STR8## are similar tothose described in Belgian Pat. No. 839,360. One route involves treatingthe corresponding nitrile (D is --CN) with hydrogen sulfide in thepresence of a basic catalyst, preferably in the presence of a solvent.Useful solvents are lower alkanols, pyridine, or preferably a dipolaraprotic solvent, such as dimethylformamide or hexamethylphosphoramide.The catalsyst is preferably a strong nitrogeneous base, particularly atertiary amine such as triethylamine, trimethylamine, or the like, or analkanolamine, such as triethanolamine, and the like. The reaction can becarried out at room temperature. It is desirable that the reactionsolution be saturated with hydrogen sulfide. Alcohols of formula RQwhere R is a group of formula IV may be prepared by reduction of thecorresponding acids, esters or aldehydes, e.g., with hydride, or byconversion of the corresponding halide to an ester, e.g., by reactionwith sodium acetate, followed by hydrolysis of the ester, or by reactionwith formaldehyde of a Gringard reagent derived from the correspondinghalide. The halides of formulas RQ where R is a group of formula IV canbe prepared by halomethylation of the compound ##STR9## or side chainhalogenation of ##STR10##

As stated earlier, the esters wherein W is OR in which R is a group offormula I-IX are useful pest control agents having the ability to knockdown insects, such as houseflies, or repel mites and/or to kill insectsor mites. The particular mode of pest control activity (high knockdown,repelling or killing action) can vary with the individualcyclopropanecarboxylate ester of the invention and thus depends on thespecific combination of acid and alcohol moieties.

The invention includes, within its scope, pest control compositionscomprising an agriculturally acceptable adjuvant--that is, at least onecarrier or a surface-active agent--and, as active ingredient, at leastone pest control ester of this invention. Likewise, the inventionincludes also a method of controlling insect, acarine or other arthropodpests at a locus which comprises applying to the pests or to the locus apest controlling effective amount of at least one ester of theinvention.

With respect to the spectrum of pesticidal activity, the compounds ofthis invention exhibit a selective or non-selective activity asinsecticides or acaricides against one or more species of such orders asColeoptera, Lepidoptera (especially larvae), Diptera, Orthoptera,Hemiptera, Homoptera and Acarina depending upon the specific combinationof acid and alcohol moieties according to the present invention. Thecompositions according to the present invention are useful forcontrolling one or more disease-carrying insects such as mosquitoes,flies and cockroaches, grain insects such as rice weevil (Sitophilusoryzae) and mites as well as agricultural noxious insects such asplanthoppers, green rice leafhopper (Nephotettix bipuntatus cinticepsUhler), diamondback moths (Plutella maculipennis Curtis), importedcabbage worm (Pieris rapae Linne), rice stem borers (Chilo suppressalisWalker), corn earworm larvae (Heliothis zea Boddie), aphids, tortrixes,leaf-miners and the like.

The pesticidal esters of the invention are used for harvested crops,horticultural application, forests, cultures in green house, andpackaging materials for foodstuffs, household applications and asectoparasiticides.

The term "carrier" as used herein means a material that may be inorganicor organic and of synthetic or natural origin with which the activecompound is mixed or forumlated to facilitate its application to theplant, seed, soil and other object to be treated, or its storage,transport or handling. The carrier may be a solid or a liquid.

Suitable solid carriers may be natural and synthetic clays andsilicates, for example, natural silicas such as diatomaceous earths;magnesium silicates, for example, talcs; magniesium aluminum silicates,for example, attapulgites and vermiculites; aluminum silicates, forexample, kaolinites, montmorillonites and micas; calcium carbonate;calcium sulfate; synthetic hydrated silicon oxides and synthetic calciumor aluminum silicates; elements such as, for example, carbon and sulfur;natural and synthetic resins such as, for example, coumarone resins,polyvinyl chloride and styrene polymers and copolymers; solidpolychlorophenols; bitumen, waxes such as beeswax, paraffin wax, andchlorinated mineral waxes; degradable organic solids, such as groundcorn cobs and walnut shells; and solid fertilizers, for example,superphosphates.

Suitable liquid carriers include solvents for the compounds of thisinvention and liquids in which the toxicant is insoluble or onlyslightly soluble.

Examples of such solvents and liquid carriers, generally, are water,alcohols, for example, isopropyl alcohol, ketones, such as acetone,methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers;aromatic hydrocarbons such as benzene, toluene and xylene; petroleumfractions, such as kerosene, light mineral oils, chlorinatedhydrocarbons, such as methylene chloride, perchlorethylene,trichloroethane, including liquified, normally vaporous, gaseouscompounds. Mixtures of different liquids are often suitable.

If used, the surface-active agent may be an emulsifying agent or adispersing agent or a wetting agent. It may be nonionic, ionic orpreferably, mixtures of both. Surface-active agents usually applied informulating pesticides may be used. Examples of such surface-activeagents are the sodium or calcium salts of polyacrylic acids and ligninsulfonic acids; the condensation products of fatty acids or aliphaticamines or amides containing at least 12 carbon atoms in the moleculewith ethylene oxide and/or propylene oxide; fatty acid esters ofglycerol, sorbitan, sucrose or pentaerythritol; fatty acid salts of lowmolecular weight, mono-, di-, and trialkyl-amines; condensates of thesewith ethylene oxide and/or propylene oxide; condensatiion products offatty alcohols or alkyl phenols, for example, p-octylphenol orp-octylcresol, with ethylene oxide and/or propylene oxide; sulfates orsulfonates of these condensation products; alkali or alkaline earthmetal salts, preferably sodium salts of sulfonated castor oil, andsodium alkylaryl sulfonates such as sodium dodecylbenzene sulfonate; andpolymers of ethylene oxide and copolymers of ethylene oxide andpropylene oxide.

The compositions of the invention may be formulated as wettable powders,dusts, granules, solutions, emulsifiable concentrates, emulsions,suspension concentrates or aerosols. Encapsulated formulations andcontrolled release formulations are also contemplated, as are baitformulations. Wettable powders are usually compounded to contain 25, 50or 75%w of toxicant and usually contain, in addition to solid carrier,3-10%w of stabilizer(s) and/or other additives such as penetrants orstickers. Dusts are usually formulated as a dust concentrate having asimilar composition to that of a wettable powder but without adispersant, and are diluted in the field with further solid carrier togive a composition usually containing 1/2-10% of toxicant. Granules maybe manufactured by extrusion of plastics, agglomeration or impregnationtechniques. Generally, granules will contain 1/2-25% w toxicant and0-10% w of additives such as stabilizers, slow release modifiers andbinding agents. Emulsifiable concentrates usually contain, in additionto the solvent, and when necessary, cosolvent, 10-50% w/v toxicant,2-20% w/v emulsifiers and 0-20% w/v of appropriate additives such asstabilizers, penetrants and corrosion inhibitors. Suspensionconcentrates are compounded so as to obtain a stable, nonsedimenting,flowable product and usually contain 10-75% w toxicant, 0-5% w ofdispersing agents, 0.1-10% w of suspending agents such as protectivecolloids and thixotropic agents, 0-10% w of appropriate additives suchas defoamers, corrosion inhibitors, stabilizers, penetrants andstickers, and as carrier, water or an organic liquid in which thetoxicant is substantially insoluble; certain organic additives orinorganic salts may be dissolved in the carrier to assist in preventingsedimentation or as antifreeze agents for water.

Aqueous dispersions and emulsions, for example, compositions obtained bydiluting a wettable powder or an emulsifiable concentrate according tothe invention with water, also lie within the scope of the presentinvention.

The compositions of the invention can also contain other ingredients,for example, other compounds possessing pesticidal, herbicidal orfungicidal properties, or attractants, such as pheromones, attractivefood ingredients, and the like, for use in baits and trap formulations.

Particularly useful compositions can be obtained by using a mixture oftwo or more kinds of the present compounds, or by the use of synergists,such as those known for use with the general class of "pyrethroid"compounds, especiallyα-[2-(2-butoxyethoxy)ethoxy]-4,5-methylenedioxy-2-propyltoluene alsoknown as piperonyl butoxide,1,2-methylenedioxy-4-[2-(octylsulfinyl)propyl]benzene,4-(3,4-methylenedioxyphenyl)-5-methyl-1,3-dioxane also known assafroxane, N-(2-ethyhexyl)bicyclo-[2,2,1]hept-5-ene-2,3-dicarboxamide,octachlorodipropylether, isobornyl thiocyanoacetate, and othersynergists used for allethrin and pyrethrin. Useful compositions can beprepared with other biological chemicals including othercyclopropanecarboxylates, organic phosphatetype insecticides andcarbamate-type insecticides.

The compositions of the invention are applied in sufficient amount tosupply the effective dosage of active ingredient at the locus to beprotected. This dosage is dependent upon many factors, including thecarrier employed, the method and conditions of application, whether theformulation is present at the locus in the form of an aerosol, or as afilm, or as discrete particles, the thickness of film or size ofparticles, the insect or acarine species to be controlled and the like,proper consideration and resolution of these factors to provide thenecessary dosage of active material at the locus being within the skillof those versed in the art. In general, however, the effective dosage ofactive ingredient of this invention at the locus to be protected--i.e.,the applied dosage--is of the order of 0.01% to 0.5% based on the totalweight of the formulation, though under some circumstances the effectiveconcentration will be as little as 0.001% or as much as 2%, on the samebasis.

Illustrative Embodiments

The invention is illustrated by the following embodiments which describethe preparation of typical species of the invention. The embodiments arepresented for the purpose of illustration only, and should not beregarded as limiting the invention in any way. The identity of theproducts, including intermediates, was confirmed by elemental, infraredand nuclear magnetic reasonace spectral (NMR) analyses as necessary.

Embodiment I (1R,cis)-2,2-Dimethyl-3-(2-(isopropoxyimino)propyl)cyclopropanecarboxylicacid

To a solution of 1.85 g of sodium bicarbonate in 50 ml of water, wereadded 1.70 g of(1R,cis)-2,2-dimethyl-3-(2-oxopropyl)cyclopropanecarboxylic acid and1.15 g of isopropoxyamine hydrochloride at room temperature. Thereaction mixture was stirred at room temperature for 4.5 hours andfiltered through celite. The filtrate was acidified with concentratedhydrochloric acid to a pH of 2, and extracted with methylene chloride.The organic extract was washed with a sodium chloride solution, driedover magnesium sulfate, stripped and concentrated under high vacuum togive the desired product as a slightly amber oil.

Embodiment II α-Cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-(-2-(isopropoxyimino)propyl)cyclopropanecarboxylat

To a stirred solution of 0.456 g of potassium carbonate and 0.005 g ofbenzyltriethylammonium chloride in 6 ml of water, was added 1.5 g of(1R,cis)-2,2-dimethyl-3-(2-(isopropoxyimino)propyl)cyclopropanecarboxylicacid, prepared as in Embodiment I above, in 10 ml of toluene, andsubsequently 1.9 g of α-cyano-3-phenoxybenzyl bromide. The resultingreaction mixture was stirred and heated at 65° C. for 2 hours. Thereaction mixture was then allowed to cool and settle for 2 days. Thetoluene phase was separated, washed successively with 25 ml of water, 10ml of saturated sodium bicarbonate, and 10 ml of saturated sodiumchloride solutions, dried over magnesium sulfate and stripped under highvacuum to give 2.8 g of a yellow oil. The oil was adsorbed on silica geland chromatographed using a mixture of pentane/ether (4:1) as the eluentto yield (a) 1.0 g of the desired product as a higher Rf isomer mixtureand (b) 0.4 g of the desired product as a lower Rf mixture of isomers.

Following procedures similar to Embodiment II above: α-cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-(2-(neopentoxyimino)propyl)cyclopropanecarboxylate,3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-(2-(isobutoxyimino)propyl)cyclopropanecarboxylate,α-cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-(2-(cyclopropylmethoxyimino)propyl)cyclopropanecarboxylate,α-cyano-3-phenoxybenzyl(1R,cis)-2,2-dimethyl-3-(2-(cyclobutylmethoxyimino)propyl)cyclopropanecarboxylateare prepared as well as the corresponding esters in the racemic and(1R,trans) form and similar esters with other alcohols:α-ethynyl-3-phenoxybenzyl alcohol, 3,4,5,6-tetrahydrophthalimidomethylalcohol, 2,6-dichlorobenzyl alcohol, 2-chloro-4-phenyl-2-butenl-o1 andallethrolone.

Embodiment III Pesticidal Activity

As an example, activity of the compounds of this invention with respectto insect and acarine pests was determined by using standardized testmethods to test the toxicity of the compounds as follows:

Corn earworm larvae (Heliothis zea (Boddie) were tested by spraying abroad bean plant with dilutions of acetone solution of test compoundinto water containing an emulsifier. Immediately after spraying, 5larvae were transferred to the plant and held for 44-46 hours, at whichtime the dead and moribund larvae were counted. The tests were conductedemploying several dosage rates for each test compound.

The toxicity of the compound of the invention was compared to to that ofa standard pesticide (Parathion), its relative toxicity then beingexpressed in terms of the relationship between the amount of compound ofthe invention and the amount of the standard pesticide required toproduce the same percentage (50) of mortality in the test insects oracarine. Assigning the standard pesticide and arbitrary rating of 100,the toxicities of the compound of the invention with that of thestandard pesticide. That is to say, a test compound having a ToxicityIndex of 50 would be half as active, while one having a Toxicity Indexof 200 would be twice as active as the standard pesticide.

The species of Embodiment II (a) of the present invention was found tohave a corn earworm toxicity value of 49 using the above procedure andthe species of Embodiment II (b) was found to have a corn earwormtoxicity value of 28.

I claim:
 1. A compound of the formula ##STR11## wherein R¹ is an alkylgroup containing from 1 to 10carbon atoms optionally substituted by oneor more halogen atoms; a (cycloalkyl)alkyl group containing from 3 to 7ring carbon atoms, a total of from 4 to 9 carbon atoms and optionallyring-substituted by one or more halogen atoms; a cycloalkyl groupcontaining from 3 to 7 ring carbon atoms; an alkenyl group containingfrom 2 to 4 carbon atoms optionally substituted by one or more halogenatoms or alkynyl group containing from 2 to 4 carbon atoms or an arylgroup containing from 6 to 12 carbon atoms or an aralkyl groupcontaining from 7 to 10 carbon atoms, each optiionally ring-substitutedby one or more halogen atoms; W is a chlorine or bromine atom or --OR inwhich R is a hydrogen atom, a salt-forming cation or an alkyl groupcontaining from 1 to 20 carbon atoms.
 2. A compound according to claim 1wherein R¹ is an alkyl group containing from 1 to 5 carbon atoms.
 3. Acompound according to claim 2 wherein R¹ is isopropyl.
 4. A compoundaccording to claim 1, 2 or 3 in the (1R,cis) form.